Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/40—Succinic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic

Definitions

• the present invention relates to novel mixtures of succinic esters based on alkyl and benzyl alcohols and their use as plasticizers for plastics.
• plasticizers are additives used in polymer processing that improve processability, flexibility and ductility. Since the plasticizers are not firmly attached to the polymer, they can migrate or volatilize.
• the plasticizers used to make soft PVC are predominantly phthalic acid esters such as the general purpose di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
• DEHP di-2-ethylhexyl phthalate
• DIDP diisononyl phthalate
• DIDP diisodecyl phthalate
• fast gelling plasticizers such as the short chain phthalates dibutyl phthalate (DBP), diisobutyl phthalate (DiBP) and benzyl butyl phthalate (BBP) may be added.
• DBP dibutyl phthalate
• DIBP diisobutyl phthalate
• BBP benzyl butyl phthalate
• phthalates are becoming increasingly limited due to legal framework conditions.
• One example is the prohibition and restriction of the use of some phthalates in the manufacture of toys and childcare articles (Directive 2005/84 / EC of the European Parliament and of the Council of 14 December 2005).
• SVHC Very High Concern
• ECHA European Chemicals Agency
• the phthalate plasticizers are based on petrochemical raw materials. In their production, greenhouse gases are set free which can be regarded as problematic in many respects.
• Plasticizers based on renewable raw materials are in the focus of attention because of the discussion on the climate, sustainability and limited availability of fossil raw materials. Plasticizers based on succinic acid could meet these requirements.
• succinic acid was identified as one of 12 sugar-based synthetic building blocks of highest value (see, for example, T. Werpy and G. Petersen et al Top Value Added Chemicals From Biomass, Volume I: Results of Screening for Potential Candidates from Sugars and Synthesis Gas, page 1)
• succinic acid esters as plasticizers for plastics has been known for some time. So describes the example DE-A 1962500 the use of dialkyl succinates, in particular succinic acid diacylate, as plasticizers for stain-resistant PVC films.
• esters of succinic acid as plasticizers for PVC is of LeCaptain et al. in Polym. Bull. (2010) 65: 589-598 in the article "Poly (vinyl chloride) plasticized with succinate esters: synthesis and characterization". There, di-octyl succinate (DOS), di-hexyl succinate (DHS), di-butyl succinate (DBS) and di-ethyl succinate (DES) are described. Infrared (IR), Differential Scanning Calorimetry (DSC), and Dynamic Mechanical Analysis (DMA) are used to qualitatively determine the compatibility of esters in PVC and their potential as phthalate replacement. Important application-related examinations and statements such as migration and volatility from the plasticized polymer or its long-term use properties are not made for the processor.
• DOS di-octyl succinate
• DHS di-hexyl succinate
• DBS di-butyl succinate
• DES di-ethyl succinate
• EP-A 1 873 198 Alkylbenzyl esters of aromatic and aliphatic polycarboxylic acids are already known which can be used as plasticizers with a low dissolution temperature for plastics.
• succinic acid esters known from the prior art do not correspond in all respects to the desired requirements for a good plasticizer, in particular with regard to plasticizer effectiveness and processability, and are still in need of improvement in this respect.
• the object of the present invention to provide new plasticizers for plastics based on succinic esters, which have improved properties, in particular with respect to the softening effect in conjunction with improved processability of the final product.
• mixtures of succinic esters based on alkyl and benzyl alcohols are particularly suitable as plasticizers for plastics, in particular as plasticizers for PVC.
• the mixtures according to the invention not only have a low dissolving temperature but are also distinguished by very good plasticizing properties Properties off.
• a low dissolution temperature is advantageous because it allows faster processing of the plastics, or processing of the plastics at lower temperatures.
• the present invention provides mixtures of succinic esters characterized in that they contain at least two compounds selected from the formulas R 1 -OC (O) -CH 2 -CH 2 -C (O) OR 1 (I) R 1 -OC (O) -CH 2 CH 2 -C (O) OR 2 (II) and R 2 -OC (O) -CH 2 -CH 2 -C (O) OR 2 (III) contain, wherein R 1 is a straight-chain or branched alkyl radical, and R 2 is an optionally substituted benzyl radical.
• R 1 represents a straight-chain or branched alkyl radical having 1 to 12 carbon atoms
• R 2 is a benzyl radical which is optionally substituted by C 1 - to C 4 -alkyl or halogen.
• R 1 represents a straight-chain or branched alkyl radical having 8 to 12 carbon atoms
• R 2 is an optionally substituted by C 1 - to C 4 -alkyl benzyl radical.
• R 1 is a straight-chain or branched alkyl radical having 8, 9, 10 or 11 carbon atoms
• Suitable straight-chain or branched alkyl radicals in the meaning of R 1 are, for example: methyl; ethyl; Propyl such as n-propyl, iso-propyl; Butyl and n-butyl, sec-butyl, isobutyl; amyl; Hexyl, such as n-hexyl, 1,4-dimethylbutyl; n-heptyl; Octyl, such as isooctyl, n-octyl, 2-ethylhexyl; Nonyl such as n-nonyl and isononyl; Decyl. such as n-decyl, isodecyl; and dodecyl as n-dodecyl and Isododecylreste and their entire different isomeric forms.
• Suitable substituted benzyl radicals in the meaning of R 2 are: methylbenzyl, dimethylbenzyl, trimethylbenzyl, ethylbenzyl, isopropylbenzyl and tert. Butylbenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, bromobenzyl, or dibromobenzyl radicals
• R 1 is 2-ethylhexyl, n-octyl, isooctyl, n-nonyl, isononyl; 3,5,5-trimethylhexyl, n-decyl, isodecyl; n-dodecyl or isododecyl and R 2 is benzyl.
• R 1 is 2-ethylhexyl, n-octyl, isooctyl, n-nonyl, isononyl; 3,5,5-trimethylhexyl, n-decyl, isodecyl; n-dodecyl or isododecyl and R 2 is benzyl.
• the amount of compound of the formula (I) is generally from 10 to 50% by weight, preferably from 15 to 35% by weight and very particularly preferably from 20 to 30% by weight, of the amount of compound of the formula (II) generally 25 to 75 wt .-%, preferably 35 to 65 wt .-% and most preferably 40 to 60 wt .-%, and the amount of compound of formula (III) generally 10 to 50 wt. -% preferably 15 to 35 wt .-% and most preferably 20 to 30 wt .-% in each case based on 100 percent of the mixture.
• mixtures of succinic alkyl esters which are characterized in that they contain the compounds of the formulas (I) and (III).
• the radicals R 1 and R 2 each have the abovementioned general and preferred meanings.
• those which are particularly preferred are those in which in the formulas (I) and (III) R 1 is 2-ethylhexyl, n-octyl, isooctyl, n-nonyl, isononyl; 3,5,5-trimethylhexyl, n-decyl, isodecyl; n-dodecyl or isododecyl and R 2 is benzyl.
• the amount of compound of the formula (I) is generally from 15 to 95% by weight, preferably from 25 to 75% by weight and very particularly preferably from 40 to 60% by weight, of the amount of compound of the formula (III) generally 85 to 5 wt .-%, preferably 75 to 25 wt .-% and most preferably 60 to 40 wt .-%, each based on 100 percent of the mixture.
• the compounds of formula (II) are novel and also subject of the present invention. Preference is given to those compounds of the formula (II) in which R 1 is 2-ethylhexyl, n-octyl, isooctyl, n-nonyl, isononyl; 3,5,5-trimethylhexyl, n-decyl, isodecyl; n-dodecyl or isododecyl and R 2 is benzyl.
• the compounds (II) are outstandingly suitable as plasticizers for plastics.
• the mixtures according to the invention can be prepared by different processes.
• the process can be carried out in one or two steps. When carried out in one step, all reactants are contacted and reacted substantially simultaneously with each other. In the reaction in two steps, the succinic acid or a derivative thereof are reacted with an alcohol in a first step, and the resulting reaction mixture is reacted with the second alcohol.
• the reaction mixture can be diluted with a solvent, which can also serve as entrainer for the discharge of water of reaction.
• a solvent which can also serve as entrainer for the discharge of water of reaction.
• the monofunctional alcohols used to form the ester can be used simultaneously as an entrainer and in excess.
• the esterification of succinic acid may be carried out with or without typical catalysts known to those skilled in the art.
• the mixtures according to the invention by reaction of the alcohols of the formulas (IV) and (V) with succinic acid halides with the elimination of hydrohalic acid.
• the alcohols of formulas (IV) and (V) can be reacted either simultaneously or sequentially.
• Benzyl chloride can also be used for benzylation instead of benzyl alcohol.
• the preparation of the mixtures according to the invention is also in other ways, as for example by mixing the individual components (I), (II) and (III) in different amounts possible.
• reaction operations described above may be followed by purification operations familiar to the person skilled in the art, such as, for example, extraction, in particular aqueous scrubbing, distillation, steam distillation, adsorption and / or filtration.
• Another object of the present invention is a process for preparing an ester mixture according to the invention containing the compounds of the formulas
• R 1 is -OC (O) -CH 2 -CH 2 -C (O) OR 1 (I), R 1 -OC (O) -CH 2 CH 2 -C (O) OR 2 (II) and R 2 is -OC (O) -CH 2 -CH 2 -C (O) OR 2 (III), wherein R 1 is a straight-chain or branched alkyl radical, and R 2 is an optionally substituted benzyl radical, which is characterized in that in a process step or in two successive process steps, two different monofunctional alcohols of the formulas R 1 -OH (IV) and R 2 -OH (V), wherein R 1 and R 2 are as above, for the formulas (I) to (III) given, general and preferred meanings, at a temperature of 50 to 250 ° C and optionally at a pressure of 2 mbar to 4 bar and optionally in the
• Suitable alcohols of the formula (IV) are, for example: methyl; ethyl; Propyl such as n-propyl, iso-propyl; Butyl and n-butyl, sec-butyl, isobutyl; amyl; Hexyl, such as n-hexyl, 1,4-dimethylbutyl; n-heptyl; Octyl, such as isooctyl, n-octyl, 2-ethylhexyl; Nonyl such as n-nonyl and isononyl; Decyl. such as n-decyl, isodecyl; and dodecyl such as n-dodecyl and isododecyl alcohol and their entire various isomeric forms.
• Suitable alcohols of the formula (V) are, for example: benzyl alcohol and alkyl-substituted benzyl alcohols such as methylbenzyl alcohol, ethylbenzyl alcohol, dimethylbenzyl alcohol, trimethylbenzyl alcohol, isopropylbenzyl alcohol, tert. Butylbenzyl alcohol, furthermore halo-substituted Benzyl alcohols such as chlorobenzyl alcohol, dichlorobenzyl alcohol, trichlorobenzyl alcohol, bromobenzyl alcohol, dibromobenzyl alcohol and the like.
• Suitable catalysts are in principle compounds of the formula MXn in which M is a metal cation selected from the group of the metals titanium, zirconium, vanadium, aluminum, iron, tin, and X is an anion selected from the group, -CO 3 2- , Cl - , Br - , I - ; -OR - where R is selected from methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, t -butyl; Carboxylates, in particular hexanoate, heptanoate, octanoate, 2-ethylhexanoate, stearate, palmitate, oxalate; and n is the oxidation number of the metal, preferably 2, 3 or 4.
• strong Brönsted acids such as sulfuric acid, acidic sulfates such as methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, hexyl sulfate but also KHSO 4 or NaHSO 4 , aromatic sulfonic acids, especially para-toluenesulfonic acid, benzenesulfonic acid can be used successfully.
• an ester mixture comprising the compounds of the formulas R 1 -OC (O) -CH 2 -CH 2 -C (O) OR 1 (I) and R 2 is -OC (O) -CH 2 -CH 2 -C (O) OR 2 (III), wherein R 1 is a straight-chain or branched alkyl radical, and R 2 is an optionally substituted benzyl radical, which is characterized in that the individual compounds of the formulas (I) and (II) are mixed together.
• R 1 is a straight-chain or branched alkyl radical
• R 2 is an optionally substituted benzyl radical
• the compound of the formula (II) is separated from the ester mixture of the formulas (I), (II), (III) or in a two-stage process acid or acid anhydride with the alcohols of the formulas (IV) and ( V) or its or synthesis equivalents are reacted sequentially, combined with a possible purification step according to step 1 or 2.
• succinic acid used to prepare the succinic acid ester mixtures of the invention has been prepared from bio-based raw materials, e.g. by a microbiological fermentation process, so impurities can be contained in the succinic acid, which can also be found in the mixtures according to the invention.
• Typical contaminants that can enter the end products due to the microorganisms used are nitrogen- and sulfur-containing compounds.
• the ester mixtures according to the invention preferably contain less than 1000 ppm by mass of nitrogen atoms and less than 50 ppm by mass of sulfur atoms, based in each case on the mixture. Particular preference is given to mixtures according to the invention which contain 0.01 to 750 ppm by weight of nitrogen atoms and 0.0001 to 40 ppm by mass of sulfur atoms, based in each case on the mixture.
• ester mixtures comprising at least two succinic acid alkyl esters of the formulas (I), (II) and (III) which are characterized in that the succinic acid alkyl esters of the formulas (I), (II) and (III) are derived from biomass resources and the mixture contains 0.01 ppm to 1000 ppm by mass of nitrogen atoms and 0.01 ppm to 50 ppm by mass of sulfur atoms, based in each case on the mixture.
• ester mixtures according to the invention can be prepared by employing alcohols of the formulas (IV) and (V) and succinic acid which originate from biomass resources and wherein the mass fraction of nitrogen atoms relative to the total mass of used alcohols and succinic acid in the range of 0.01 ppm to 1000 ppm and the mass fraction of sulfur atoms based on the total mass of alcohols and succinic acid used in the range of 0.01 ppm to 50 ppm.
• the new succinic acid ester mixtures are outstandingly suitable as plasticisers for plastics.
• Another object of the invention is the use of a succinate ester mixture according to the invention as a plasticizer for plastics.
• Suitable plastics include, for example, polyvinyl chloride (PVC), vinyl chloride-based copolymers, polyvinylidene chloride, polyvinyl acetals, polyvinyl butyral, polyacrylates, polymethacrylates, polyalkyl methacrylates, e.g.
• PVC polyvinyl chloride
• vinyl chloride-based copolymers polyvinylidene chloride
• polyvinyl acetals polyvinyl butyral
• polyacrylates polymethacrylates
• polyalkyl methacrylates e.g.
• the succinic acid ester mixtures according to the invention are preferably used as plasticizers and processing aids for PVC and polyacrylates.
• the plastics produced with the new plasticizers are characterized by a low hardness and high flexibility in comparison to the plastics known from the prior art with plasticizers based on one-component succinic esters.
• the amount of plasticizer can be reduced cost-effectively in comparison with the use of the known and less efficient, symmetrical succinic esters. Also, the savings of plasticizers or the reduction of the amount of plasticizer used mean better final product properties in terms of volatility and migration of the plasticizer.
• the invention also provides the use of the succinic acid ester mixtures according to the invention as processing aids and plasticizers in adhesives, adhesive components, adhesive sealants, adhesive sealant components, sealants, sealant components, or coating compositions, in paints, inks or paints, in plastisols including PVC plastisols, and as plasticizers in plastics or plastic components, preferably in polyvinyl chloride.
• Another object of the present invention are softener preparations comprising a succinate ester mixture according to the invention and optionally further conventional additives.
• additives include other plasticizers, stabilizers, antioxidants, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, kickers, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents or biostabilizers.
• plasticizers according to the invention are generally used for 10 to 200 parts, preferably for 20 to 150 parts, each to 100 parts of plastic.
• the new softener formulations enable the production of end products with good low temperature properties.
• the mixtures according to the invention are preferably used for the production of plastisols, preferably of plastisols based on PVC. Used in PVC plastisols, the low-viscosity succinic acid ester mixtures allow the production of low-viscosity, storage-stable plastisols.
• plastics produced using the plasticizer formulations according to the invention may also contain, in addition to the plasticizer formulations according to the invention, other suitable auxiliaries and additives.
• suitable auxiliaries and additives examples include further plasticizers, stabilizers, antioxidants, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, kickers, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents or biostabilizers.
• the present invention further relates to a process for the production of plasticized plastics, in particular softened PVC, which is characterized in that in a first step PVC, in particular emulsion and microsuspension PVC, at 10 to 60 ° C with the softener preparation according to the invention and optionally mixed further auxiliaries and additives, wherein 10 to 200 parts of the plasticizer according to the invention are used per 100 parts of plastic. In a second step, this plastisol is brought into shape and processed at temperatures of 140 to 200 ° C to the final article.
• PVC in particular emulsion and microsuspension PVC
• the dissolution temperature was considered to be reached if, for 3 minutes consecutively, no increase in the permeability value by the photocell was registered and the polyvinyl chloride was dissolved. Upon reaching the temperature of the beaker contents of 200 ° C, the measurement was stopped. A low dissolution temperature indicates good compatibility of the plasticizer and softener formulations with polyvinyl chloride and is an indicator of rapid processability.
• a plasticizer-containing PVC powder mixture was homogenized and gelled on a two-roll mill; then the compound was pressed into test plates and the hardness was determined with a Zwick Shore Hardener.
• the hardness (Shore A) was measured on smooth and flat test specimens of dimensions 6 mm ⁇ 40 mm ⁇ 50 mm.
• Low Shore A hardness means softer products and is a measure of the efficiency of the plasticizers.
• the rolled skin was removed. After portioning, specimens of dimension 6 mm ⁇ 40 mm ⁇ 50 mm were pressed. The temperature of the press was 170 ° C; the pressing time was 10 minutes in total, of which 7 minutes heating phase with a pressure ⁇ 10 bar and 3 minutes pressing time under high pressure> 100 bar. After cooling under pressure in a cooling press to a maximum of 30 ° C, the test specimens were removed from the mold. After a minimum of 24 hours of storage at 23 ° C., the test specimens were used to determine the Shore A hardness with a Zwick type H04.3150 in accordance with DIN 53505 at five different points, taking the average value into account.
• the Shore A hardness of test specimens containing in each case 60 phr of plasticizer was determined.
• a lower Shore A hardness value is a statement about the good plasticizing property (efficiency) of the plasticizer.
• the dissolution temperatures were determined.
• the dissolution temperature serves as proof of the compatibility of a plasticizer with the respective plastics or polymers.
• a low dissolution temperature in this case indicates good compatibility of the plasticizer with polyvinyl chloride and rapid processability.
• the ester mixtures according to the invention have good plasticizing properties combined with a low dissolving temperature.
• the ester mixtures according to the invention can be used as efficient plasticizers, which also allow processing of the PVC at low temperatures, which in turn leads to energy savings and shorter times in the manufacturing cycles.
• the use of the inventive softener mixtures surprisingly allows for softer products or a cost-efficient reduction of the plasticizer content to obtain products having the same hardness. Less use of the potentially migrating or volatile plasticizers allows the production of end products with better volatility and migration properties of the plasticizer.
• the comparison of Example 7 and 7a shows the positive effect of the benzyl radical in the mixture according to the invention benzyl 1-dodecylsuccinate hardness and dissolution temperature compared with the di-1-dodecylsuccinate.

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• 2012
  • 2012-02-24 EP EP20120156807 patent/EP2631266A1/fr not_active Withdrawn
• 2013
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